Hexahydro-1,3,5-triazines

ABSTRACT

A condensation product of an aldehyde, particularly formaldehyde which may be generated in situ, and an ether-amine of the formula HOCmH2m(OCnH2n)pNH2 where m, n and p are integers, particularly 2-(2&#39;&#39;-hydroxyethoxy)ethylamine, is a biocide which is particularly effective against the microbes which attack hydrocarbon fractions, for example jet fuel, in the presence of water, the amount of which water may be very small. The biocide is especially useful as an additive in cutting or soluble oil emulsions to mitigate their degradation by micro-organisms.

United States Patent [191 Limaye et a1.

[ HEXAHYDRO-1,3,5-TRIAZINES [73] Assignee: Coalite and Chemical ProductsLimited, Chesterfield, England [22] Filed: Mar. 22, 1973 [21] Appl. No.:343,989

[30] Foreign Application Priority Data Mar. 24, 1972 United Kingdom13894/72 [52] US. Cl 260/248 NS; 424/249; 44/63;

[51] Int. Cl. C07D 251/04 [58] Field of Search 260/248 NS [56]References Cited UNITED STATES PATENTS 2,675,382 4/1954 Melamed 260/248X 2,889,277 6/1959 Hughes 260/248 X Frankel..... Frankel.....

[ Oct. 28, 1975 Primary Examiner-John M. Ford Attorney, Agent, orFirmW0odhams, Blanchard and Flynn [5 7 ABSTRACT A condensation productof an aldehyde, particularly formaldehyde which may be generated insitu, and an ether-amine of the formula HOC,,,l-l [OC,,H ,,],,NH wherem, n and p are integers, particularly 2-(2'- hydroxyethoxy)ethylamine,is a biocide which is particularly effective against the microbes whichattack hydrocarbon fractions, for example jet fuel, in the presence ofwater, the amount of which water may be very small. The biocide isespecially useful as an additive in cutting or soluble oil emulsions tomitigate their degradation by micro-organisms.

4 Claims, No Drawings HEXAHYDRO-l,3,5-TRIAZINES The invention relates toa biocide or disinfectant, to a method of producing the biocide and to acomposition comprising the biocide.

It is known that various liquid compositions used in industry andcomprising organic components, for example hydrocarbon fractions such asjet fuel, fuel oil and other petroleum fractions, and cutting oils, aresubject to attack by microorganisms in the presence of water. The amountof water which is present may be very small indeed.

Thus, oils and oil emulsions used in the engineering industry aslubricants and coolants are, after use, invariably found to becontaminated by micro-organisms. The degree and speed of build-up ofcontamination is so high that a fresh emulsion shows, after 5 to 6 daysuse, hundreds of thousands or even millions of organisms per ml. of theemulsion. These organisms in turn change the chemical as well as thephysical properties of the oil emulsion.

At the beginning of degradation of the oil emulsion by themicro-organisms, oil droplets of approximately 1 micron size and whichare evenly dispersed in the emulsion begin to increase in diameter up to10 12 microns and, after a while, free oil separates out and can beobserved as a separate layer of oil on the surface of the oil emulsion.The emulsion is at times discoloured and it frequently generates a badodour.

The degradation of the emulsion ultimately results in:

1. loss in the lubricating film;

2. loss in the anticorrosive properties of the emulsion;

3. fall in the pH of the emulsion;

4. reduction in the useful life of the oil emulsion;

5. accum ilation of slime and sediment;

6. impairment of the finish of the metal being machined; I and 7. lossin the useful properties of the oil emulsion clue to degradation ofadditives which give the tool bite and degradation of emulsifiers.

These and other undesirable changes are brought about by the activity ofmicro-organisms in oils and oil emulsions, though in straight oils, orin insoluble oils, the rate of degradation is slower. This microbialattack compels the user to discard the contaminated cutting oil oremulsions and to recharge with fresh cutting oil or emulsion. Thisinvolves not only a financial loss but also slows down the productionrate.

It is an object of the invention to provide a biocide which whenincluded in small quantities in such oil emulsions, will mitigatedegradation of the emulsion by micro-organisms without any substantialdeleterious effect upon other properties of the oil emulsion.

According to the invention there is provided a condensation product ofan aldehyde and an ether-amine of the formula HOCmHml n zn lp z in whichm, n and p are integers. Advantageously, m, n and p each denote integersfrom 1 to 6. It will be understood that when either of m and n isgreater than 1, the corresponding group C I-l or C l-1 may be a straightor branched chain.

The condensation reaction mixture may also include a primary alkylaminewhich preferably does not contain more than four carbon atoms in themolecule and- /or a primary cycloalkylamine, particularlycyclopentylamine or cyclohexylamine, the ether-amine and the alkylamineand/or cycloalkylamine being present in such amounts that thecondensation reaction product contains residues derived from theether-amine and from the alkylamine or cycloalkylamine. A preferredalkylamine is ethylamine and the preferred cycloalkylamine iscyclohexylamine.

Preferred ether-amines thoxy) ethylamine HO CH CH 0 CH CH NH Othersuitable ether-amines include 2-(3'-hydroxypropoxy)ethylamine, 2-( 1-methyl-2'-hydroxyethoxy)ethylamine, 3-(2-hydroxyethoxy) propylamine, 3-(3-hydroxypropoxy )propylamine, 2-(4-hydroxybutoxy)ethylarnine and3-(2'-hydroxyethoxy)-lmethylpropylamine.

The aldehyde precursor of the condensation product is advantageously analiphatic aldehyde, for example an aliphatic aldehyde containing notmore than four carbon atoms in the molecule. The preferred aldehyde isformaldehyde and it may be generated in the reaction mixture from, forexample, paraformaldehyde.

The condensation reaction is readily carried out at a slightly elevatedtemperature, conveniently at a temperature in the range 40 60C. Suitablythe amine or mixture of amines, neat or in aqueous solution, iscondensed with paraformaldehyde whilst maintaining the temperature below60C, the water of reaction together with any used as solvent being thenremoved, for example as an azeotrope with a suitable, addedazeotropeformer such as toluene. The aldehyde and amine (or aminemixture) are preferably used in substantially equimolar amounts, forexample from 0.8 to 12 moles of amine or amine mixture per mole ofaldehyde.

The invention also includes a biocide which is a substitutedhexahydro-l,3,5-triazine of the formula include 2-( 2 -hydroxyein whichR is hydrogen or an alkyl group, at least one of the R groups has theformula in which m, n and p are as hereinbefore defined, and the twoother R groups are groups of the same general formula or are alkyl orcycloalkyl groups. When one or two of the groups R are alkyl groups andone or more of the R groups are alkyl groups, each such groupadvantageously contains not more than four carbon atoms.

In the preferred triazines, each R is hydrogen. A particularly preferredtriazine is l,3,5-tris(2-hydroxyethoxyethyl)-hexahydro-l,3,5-triazine.Other suitable triazines include those in which one or two of thehydroxyethoxyethyl groups are replaced by C C alkyl groups and/orcycloalkyl, specifically cycohexyl or cyclopentyl, groups and/or byother hydroxyalkoxyalkyl groups as well as those in which the threehydroxyethoxyethyl groups are replaced by other hydroxyalkoxyalkylgroups. Such other hydroxyalkoxyalkyl groups are suitably those derivedfrom the ether-amines hereinbefore specifically named.

Examples of such other suitable triazines include 1- ethyl 3,5-bis(2'-hydroxyethoxyethyl)-, l-n-butyl 3,5 -bis(2-hydroxyethoxyethyl)-,l-cyclohexyl 3,5 bis(- 2'- hydroxyethoxyethyl)-, l-methyl 3,5 bis(2-hydroxypropoxyethyl)-, 1 isopropyl 3,5 bis(2'- hydroxypropoxyethy1)-, lethyl 3,5 bis(1-methyl 2 hydroxyethoxyethyl)-, 1 cyclohexyl 3,5 bis[3'(2" hydroxyethoxy)propyl] l ethyl 3,5 bis [2' (4" hydroxybutoxy)ethyl] 1propyl 3,5 bis [3 (3" hydroxypropoxy)propyl] 1 ethyl 3,5 bis [3 (2"hydroxyethoxy) l methylpropyl] 1,3 diethyl 5 (2 hydroxyethoxyethyl)-,1,3 dicyclohexyl 5 (2' hydroxyethoxyethyl)-, 1 ethyl 3 cyclohexyl 5 (2'hydroxyethoxyethy1)-, 1,3 diisopropyl 5 -(2-hydroxyethoxyethyl),1 ,3diethyl 5 [2- (3"-hydroxypropoxy)ethyl] and 1 ethyl 3 propyl 5[2-hydroxyethoxyethyl] 1 ethyl 3 (2'-hydroxyethoxyethyl)- 5(2-hydroxypropoxyethyl)-, 1 cyclohexyl 3 (2'-hydroxyethoxyethyl) 5 (2'-hydroxypropoxyethyl)-, 1 propyl 3 [3'-(2"-hydroxyethoxy)propyl] 5(2-hydroxyethoxyethyl)- and 1 ethyl 3 (2 hydroxyethoxyethyl) 5 [3'-(3"-hydroxypropoxy) propyl]- hexahydro 1,3,5 triazines.

It will be appreciated that the triazines are or form part of thecondensation products or members of the group of condensation productshereinbefore described and constituting part of the invention. Thetriazines may be obtained by the condensation of the appropriatealdehyde and amine or amine mixture in the manner hereinbeforedescribed.

The invention also includes a liquid composition containing the biocide,that is, the condensation product or the triazine.

The liquid composition may be a hydrocarbon fraction, for example a jetfuel, containing 0.001 2% v/v, preferably 0.01 0.5% v/v, of the biocide.

A further liquid composition according to the invention comprises water,a surfactant for example, a detergent, emulsifier or wetting agent, andthe biocide.

Another and preferred liquid composition according to the invention is acutting oil or oil emulsion comprising the biocide. When the oilemulsion is in a form EXAMPLE Paraformaldehyde (30g) was slowly added to2-(2'- hydroxyethoxy)ethylamine (105g) whilst stirring and maintainingthe temperature at below C. When addition of the amine was complete, themixture was maintained at 60C for some time to complete the reaction.The product was then filtered to give a waterwhite viscous fluid. Thismaterial was used in the biocide tests hereinafter given. In anotherrun, the product was dried by azeotroping it with 3 4 times its volumeof toluene. The toluene was distilled off under reduced pressure and theanhydrous product was distilled, boiling at 92C at 1mm mercury.

Contaminated cutting oil emulsions were examined micro-biologically, andthe variety of micro-organisms found included different strains ofPseudomonas, yeasts, moulds, Nocardia and anaerobes such as Clostridiumand Desulphovibrio.

The main aerobic bacteria found were Pseudomonas. The specificcontaminants were isolated in the laboratory from contaminated oils andoil emulsions and were grown on specific media and in turn were used toartificially contaminate fresh oil emulsions. 1 ml of this artificiallycontaminated sample was mixed with 8 ml of sterile distilled water 1 mlof 1% Corexit in a sterile test tube to make the initial dilution 1 10.Serial dilutions were made and a count of the number of organisms per mlwas made using conventional bacteriological techniques. The biocideproduced in the Example was added at 0.05%, 0.1% 0.2% concentrations inthree different cutting oil emulsions, namely Prosol 67, Dromus oil Band Dromus Fluid H, and incubated at 30C. The biocide-containing cuttingoil emulsions were sampled out after 24 hours, 48 hours, 120 hours, 7days, 14 days and 35 days to estimate the number of survivors. Visiblephysical changes, if any, such as discolouration, breakdown of emulsion,sedimentation, accumulation of oil droplets on the surface were alsonoted.

The biological results are shown in the following table. Experiment 1was carried out with Prosol 67 (5% emulsion concentration), Experiment 2with Dromus oil B and Experiment 3 with Dromus Fluid l-l. Experiments 4and 5 were also carried out with Prosol 67 (5% emulsion strength) but ona circulating machine simulating, as far as possible, shop floorconditions.

Colony count per ml.

Day 14 Day 35 Expt. Cone. Day 0 Day 1 Day 2 Day 5 Day 7 0.1% 108 X10 100100 100 100 100 2 0.1% 6 X 10" 100 N.T. N.T. 100 100 3 0.1% 8 X 10 100N.T. N.T. 100 100 4 0.1% 6.1 X 10 100 N.T. N.T. N.T. 100 100 Conc.denotes the biocide concentration, v/v, in the oil emulsion. The columnheaded "Day 0" gives the colony count of the initial inoculum. N.T.Means not tested". The dash indicates complete kill.

ready for use on a lathe or other metal-working machine, theconcentration of the biocide is suitably from 0.01 2% v/v, preferably0.05 1% v/v. When the cutting or soluble oil is in the form of aconcentrate, it will be understood that the concentration of the biocideis correspondingly higher, for example from 1 10% v/v.

The invention is illustrated in the following example.

No undesirable physical change was observed in the biocide-containingoil emulsion. The Herbert corrosion test indicated that theanti-corrosive properties of the emulsion were also improved by thepresence of the biocide. It will be noted from the table that in eachcase more than 99% kill was shown in 24 hours.

We claim:

1. A compound having the formula 3 ,9 15,970 5 6 if R is hydrogen oralkyl having one to four carbon atoms, and R is HOC H -{-OC, H alkylhaving one to four carbon atoms, cyclohexyl or cyclopentyl, with theproviso that at least one R is N R R 5 m 2m 7l 27dT) K H wherein m, nand p are integers from 1 to 6.

2. A compound according to claim 1 in which each y H R R R is hydrogen.

3. A compound according to claim 1 in which each R 10 is HOC H +OC,,H

4. 1,3 ,5-tris( 2 '-hydroxyethoxyethyl )-hexahydro- 1,3 ,S-triazine.

wherein

1. A COMPOUND HAVING THE FORMULA
 2. A compound according to claim 1 inwhich each R'' is hydrogen.
 3. A compound according to claim 1 in whicheach R is HOCmH2m -OCnH2n)p. 4.1,3,5-tris(2''-hydroxyethoxyethyl)-hexahydro-1,3,5-triazine.